Cosmetic or dermatological light-protective formulation comprising a water-soluble UV filter substance and a benzoxazole derivative

ABSTRACT

The invention is a light-protective cosmetic or dermatological preparation comprising (a) at least one water-soluble UV-filter substance and (b) at least one benzoxazole derivative. The invention is also a cosmetic or dermatological preparation comprising at least one water-soluble UV-filter substance and at least one benzoxazole derivative of a specified chemical structure. The invention is also a method of treating or preventing cosmetic or dermatological changes in the skin, a method of tanning or accelerating tanning of the skin, and a method of protecting the skin against light-induced aging, each comprising applying the cosmetic or dermatological preparation to the skin. The invention also includes a wipe impregnated with the preparation.

CROSS-REFERENCE TO RELATED APPLICATIONS

This is a continuation application of PCT/EP02/14296, filed Dec. 16,2002, which is incorporated herein by reference in its entirety, andalso claims the benefit of German Priority Application No.101 62 840.4,filed Dec. 20, 2001.

FIELD OF THE INVENTION

The present invention relates to cosmetic and dermatologicallight-protective preparations, in particular it relates to cosmetic anddermatological formulations with increased UV-A protection performance.

BACKGROUND OF THE INVENTION

The harmful effect of the ultraviolet part of solar radiation on theskin is generally known. Depending on their particular wavelength, therays have different effects on the skin as an organ:

The so-called UV-C radiation with a wavelength between 100 and 280 nm isabsorbed by the ozone layer in the Earth's atmosphere and accordingly isnot found in the solar spectrum. It is therefore of no physiologicalimportance during sunbathing.

The so-called UV-B region is between 290 nm and 320 nm. UV-B rays areessentially responsible for the long-lasting tanning of the skin, butcan at the same time cause an erythema, simple sunburn or even burns ofgreater or lesser severity. Chronic photodamage, photodermatoses andHerpes solaris can also be caused by UV-B radiation.

It has for a long time been incorrectly assumed that long-wave UV-Aradiation with a wavelength between 320 nm and 400 nm only has anegligible biological effect and that, correspondingly, the UV-B raysare responsible for most photodamage to the human skin. However, in themeantime, numerous studies have studied that UV-A radiation is much morehazardous than UV-B radiation with regard to the triggering ofphotodynamic, specifically phototoxic reactions and chronic changes inthe skin. The harmful influence of UV-B radiation can also be furtherintensified by UV-A radiation.

Thus, it has, inter alia, been found that even UV-A radiation sufficesunder very normal everyday conditions to harm, within a short time, thecollagen and elastin fibers which are of essential importance for thestructure and strength of the skin. The consequences are chronicphoto-induced changes in the skin—the skin “ages” prematurely. Theclinical appearance of skin aged by light includes, for example,wrinkles and lines, and also an irregular, furrowed relief. In addition,the parts affected by photo-induced skin aging have irregularpigmentation. The formation of brown spots, keratoses and evencarcinomas or malignant melanomas is also possible. Skin agedprematurely by everyday UV exposure is, moreover, characterized by loweractivity of the Langerhans cells and slight, chronic inflammation.

Approximately 90% of the ultraviolet radiation which reaches the Earthconsists of UV-A rays. While UV-B radiation varies widely depending onnumerous factors (e.g. time of year and time of day or degree oflatitude), UV-A radiation remains relatively constant day to dayirrespective of the time of year and time of day or geographicalfactors. At the same time, the majority of UV-A radiation penetratesinto the living epidermis, while approximately 70% of UV-B rays areretained by the horny layer.

The relatively recent findings concerning the effect of UV-A rays on theskin have led to increased attention now being devoted to protectivemeasures for this ray range. In practice, no sunscreen product iscomplete any more without an effective UV-A filter effect, and pure UV-Bfilter preparations are rare.

When applying a sunscreen to the skin, the ultraviolet rays can beweakened through two effects: firstly, by reflection and scattering ofthe rays at the surface of pulverulent solids (physicallight-protective) and, secondly, by absorption on chemical substances(chemical light-protective). Depending on which wavelength region isabsorbed, a distinction is made between UV-B filters (absorption range280 to 320 nm), UV-A filters (absorption range 320 to 400 nm) andbroadband filters (absorption range 290 to about 380 nm).

To protect against UV-B radiation, numerous compounds are known, theabsorption maximum of which should be around 308 nm as far as possiblesince this is the highest erythema effectiveness of solar radiation.Typical UV-B filters are, for example, derivatives of3-benzylidenecamphor, of 4-aminobenzoic acid, of cinnamic acid, ofsalicylic acid, of benzophenone, and also of 2-phenylbenzimidazole.

Some compounds are also known for protecting against UV-A radiation,such as, in particular, dibenzoylmethane derivatives. However,dibenzoylmethane derivatives are generally not photostable, as a resultof which cosmetic or dermatological preparations with a content of thissubstance should also comprise certain UV stabilizers. Further knownUV-A filter substances are certain water-soluble, sulfonated UV filtersubstances, such as, for example,phenylene-1,4-bis(2-benzimidazyl)-3,3′-5,5′-tetrasulfonic acid and itssalts.

Besides the pure UV-A or UV-B filters, there are substances which coverboth regions. This group of broadband filters includes, for example,asymmetrically substituted s-triazine compounds, such as, for example,2,4-bis{[4-(2-ethylhexyloxy)-2-hydroxy]phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine(INCl: BisEthylhexyloxyphenol Methoxyphenyl Triazine), certainbenzophenones, such as, for example, 2-hydroxy-4-methoxybenzophenone(INCl: Benzophenone 3) or2,2′-methylenebis(6-(2H-benzotriazole-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol)(INCl: Methylene Bis-Benzotriazolyl Tetramethylenebutylphenol).

In general, the light absorption behavior of light-protective filtersubstances is very well known and documented, especially as there arepositive lists for the use of such substances in most industrializedcountries, which impose very strict standards on the documentation.Since, in order to characterize a filter substance, not only is theposition of the absorption maximum important, but primarily theabsorption range, absorption spectra are recorded for each substance.However, the absorbance values can at best be a guide for theconcentration of the substances in the finished formulations sinceinteractions with ingredients of the skin or of the surface of the skinitself may give rise to imponderables. In addition, it is usuallydifficult to estimate beforehand how uniformly and thickly the filtersubstance is distributed in and on the horny layer of the skin.

To test the UV-A protection performance, use is usually made of the IPDmethod (IPD≡immediate pigment darkening). Similarly to the determinationof the sun protection factor, this method gives a value which indicateshow much longer the skin protected with the light-protective compositioncan be irradiated with UV-A radiation until the pigmentation whichoccurs is the same as for the unprotected skin.

The use concentration of known light-protective filter substancespresent in the form of a solid, which exhibit a high filter effect inthe UV-A region is, however, often limited—especially in combinationwith other substances to be dissolved. This therefore gives rise tocertain technical difficulties relating to formulation in achievingrelatively high sun protection factors or UV-A protection performance.

Since light-protective filter substances are generally expensive andsince some light-protective filter substances are also difficult toincorporate into cosmetic or dermatological preparations in relativelyhigh concentrations, it was an object of the invention to arrive, in asimple and cost-effective manner, at preparations which, despite havingunusually low concentrations of conventional UV-A light-protectivefilter substances, nevertheless achieve an acceptable or even high UV-Aprotection performance.

Most sunscreens are applied in the vicinity of water or during sportingactivity (perspiration), for which reason the water resistance of suchformulations is attributed particular importance. Children in particularlike splashing around in water and can only be kept away from it withdifficulty, to finish playing in time to avoid sunburn. Accordingly,water-resistant preparations are advisable particularly for childrensince water-resistant sunscreens also protect the user from sunburnduring bathing.

However, many of the UV filter substances which are advantageous per seare water-soluble, meaning that they are only of limited suitability forthe preparation of water-resistant sunscreen products.

A further object of the present invention was therefore to findwater-resistant cosmetic or dermatological light protection preparationswhich are characterized in particular by high UV-A protection.

SUMMARY OF THE INVENTION

It was surprising and could not have been foreseen by the person skilledin the art that light-protective cosmetic or dermatologicalpreparations, characterized in that they comprise

(a) at least one water-soluble UV filter substance and

(b) at least one benzoxazole derivative, would overcome thedisadvantages of the prior art.

The preparations according to the invention are entirely satisfactorypreparations in every respect, which are not restricted to a limitedchoice of raw materials. Accordingly, they are particularly suitable asbases for preparations with diverse application purposes. Thepreparations according to the invention exhibit very good sensory andcosmetic properties, such as, for example, extensibility on the skin orthe ability to be absorbed into the skin, and are further characterizedby very good light-protective effectiveness, an exceptionally high UV-Aprotection performance, and by excellent skin compatibility coupled withexcellent skincare data.

The invention therefore also provides light-protective cosmetic ordermatological preparations, characterized in that they comprisesynergistic substance combinations of

(a) at least one water-soluble UV filter substance and

(b) at least one benzoxazole derivative, where the UV protectionperformance, in particular the UV-A protection performance, of thesepreparations is increased supraproportionally.

Surprisingly, the substance combinations according to the invention actsynergistically, i.e. superadditively relative to the individualcomponents. They are photostable without further additives and exhibit asurprisingly high protective performance in the UV-A region.

The preparations according to the invention are further characterized bya surprisingly high water resistance.

The invention therefore also provides water-resistant light-protectivecosmetic or dermatological preparations, characterized in that theycomprise

(a) at least one water-soluble UV filter substance and

(b) at least one benzoxazole derivative.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

For the purposes of the present invention, advantageous benzoxazolederivatives are characterized by the following structural formula,

in which R¹, R² and R³, independently of one another, are chosen fromthe group of branched or unbranched, saturated or unsaturated alkylradicals having 1 to 10 carbon atoms. It is particularly advantageousaccording to the invention to choose the radicals R¹ and R² to be thesame, in particular from the group of branched alkyl radicals having 3to 5 carbon atoms. It is also particularly advantageous for the purposesof the present invention if R³ is an unbranched or branched alkylradical having 8 carbon atoms, in particular the 2-ethylhexyl radical.

A benzoxazole derivative which is particularly preferred according tothe invention is2,4-bis[5-1(dimethylpropyl)benzoxazol-2-yl-(4-phenyl)imino]-6-(2-ethylhexyl)imino-1,3,5-triazinewith the CAS No. 288254-16-0, which is characterized by the structuralformula

and is available from 3V Sigma under the trade name Uvasorb® K2A.

The benzoxazole derivative or derivatives are advantageously indissolved form in the cosmetic preparations according to the invention.In some instances, however, it may, also be advantageous if thebenzoxazole derivative or derivatives are present in pigmentary, i.e.undissolved, form—for example in particle sizes of from 10 nm to 300 nm.

The total amount of one or more benzoxazole derivatives in the finishedcosmetic or dermatological preparations is advantageously chosen fromthe range from 0.01% by weight to 20% by weight, preferably from 0.1 to10% by weight, in each case based on the total weight of thepreparations.

Advantageous water-soluble UV filter substances for the purposes of thepresent invention are sulfonated UV filters, in particular:

Phenylene-1,4-bis(2-benzimidazyl)-3,3′-5,5′-tetrasulfonic acid, which ischaracterized by the following structure:

and its salts, particularly the corresponding sodium, potassium ortriethanolammonium salts, in particular thephenylene-1,4-bis(2-benzimidazyl)-3,3′-5,5′-tetrasulfonic acidbis-sodium salt.

with the INCl name Disodium Phenyl Dibenzimidazole Tetrasulfonate (CASNo.: 180898-37-7), which is available, for example, under the trade nameNeo Heliopan AP from Haarmann & Reimer.

Also advantageous for the purposes of the present invention are1,4-di(2-oxo-10-sulfo-3-bornylidenemethyl)benzene (also:3,3′-(1,4-phenylenedimethylene)bis(7,7-dimethyl-2-oxobicyclo[2.2.1]hept-1-ylmethanesulfonicacid) and salts thereof (particularly the corresponding 10-sulfatocompounds, in particular the corresponding sodium, potassium ortriethanolammonium salt), which is also referred to asbenzene-1,4-di(2-oxo-3-bornylidenemethyl-10-sulfonic acid) and ischaracterized by the following structure:

Benzene-1,4-di(2-oxo-3-bornylidenemethyl-10-sulfonic acid) has the INClname Terephthalidene Dicamphor Sulfonic Acid (CAS No.: 90457-82-2) andis available, for example, under the trade name Mexoryl SX from Chimex.

Further advantageous water-soluble UV-B and/or broadband filtersubstances for the purposes of the present invention are, for example,sulfonic acid derivatives of 3-benzylidenecamphor, such as, for example,4-(2-oxo-3-bornylidenemethyl)-benzenesulfonic acid,2-methyl-5-(2-oxo-3-bornylidenemethyl)sulfonic acid and salts thereof.

The total amount of one or more water-soluble UV filter substances inthe finished cosmetic or dermatological preparations is advantageouslychosen from the range 0.01% by weight to 20% by weight, preferably from0.1 to 10% by weight, in each case based on the total weight of thepreparations.

It is particularly advantageous to choose the weight ratios of thebenzoxazole derivative or derivatives to the water-soluble UV filtersubstance or substances as 30:1 to 1:30, preferably as 10:1 to 1:10,particularly preferably as 5:1 to 1:5.

Besides comprising one or more oil phases, the preparations for thepurposes of the present invention may preferably additionally compriseone or more water phases and be present, for example, in the form ofW/O, O/W W/O/W or O/W/O emulsions.

Such formulations can preferably also be microemulsions, sticks,mousses, solids emulsions (i.e. emulsions which are stabilized bysolids, e.g. Pickering emulsions), sprayable emulsions orhydrodispersions. Furthermore, the preparations may advantageously alsobe oil-free or aqueous/alcoholic solutions.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

Sprayable Emulsions, in Particular Microemulsions

For the purposes of the present invention, sprayable O/W emulsions, inparticular O/W microemulsions, are particularly advantageous.

The droplet diameters of the customary “simple”, i.e. non-multiple,emulsions are in the range from about 1 μm to about 50 μm. Such“macroemulsions” are, without further coloring additives, multi-white incolor and opaque. Finer “macroemulsions”, the droplet diameters of whichare in the range from about 0.5 μm to about 1 μm, are, again withoutcoloring additives, bluish-white in color and opaque. Such“macroemulsions” usually have a high viscosity.

The droplet diameter of microemulsions for the purposes of the presentinvention, by contrast, is in the range from about 50 to about 500 nm.Such microemulsions are bluish-white in color to translucent and in mostcases of low viscosity. The viscosity of many microemulsions of the O/Wtype is comparable with that of water.

An advantage of microemulsions is that active ingredients can be presentin an essentially more finely disperse form in the disperse phase thanin the disperse phase of “macroemulsions”. A further advantage is that,due to their low viscosity, they are sprayable. If microemulsions areused as cosmetics, corresponding products are characterized by highcosmetic elegance.

Advantageous according to the invention are, in particular, O/Wmicroemulsions which are obtainable using the so-called phase-inversiontemperature technology and comprise at least one emulsifier (emulsifierA), which is chosen from the group of emulsifiers with the followingproperties:

-   -   their lipophilicity is dependent on the temperature, such that        by increasing the temperature the lipophilicity increases, and        by reducing the temperature the lipophilicity of the emulsifier        decreases.

Advantageous emulsifiers A are, for example, polyethoxylated fatty acids(PEG-100 stearate, PEG-20 stearate, PEG-150 laurath, PEG-8 distearateand the like), polyethoxylated fatty alcohols (cetearath-12,cetearath-20, isoceteth-20, beheneth-20, laureth-9 etc.), or alkylpolyglycosides (cetearyl glycoside, stearyl glycoside, palmitylglycoside etc.).

If the phase inversion is triggered essentially by varying thetemperature, O/W emulsions, in particular O/W microemulsions, areobtainable where the size of the oil droplets is determined essentiallyby the concentration of the emulsifier or the emulsifiers used, in sucha way that a higher emulsifier concentration results in relatively smalldroplets, and a lower emulsifier concentration results in relativelylarge droplets. The droplet sizes are usually between 20 and 500 nm.

For the purposes of the present invention, it is in some instancesadvantageous to use further W/O or O/W emulsifiers which do not fallunder the definition of emulsifer A, for example in order to increasethe water resistance of the preparations according to the invention. Forexample, alkylmethicone copolyols or alkyldimethicone copolyols (inparticular cetyl dimethicone copolyol, lauryl methicone copolyol), W/Oemulsifiers (such as, for example, sorbitan stearate, glyceryl stearate,glycerol stearate, sorbitan oleate, lecithin, glyceryl isostearate,polyglyceryl-3 oleate, polyglyceryl-3 diisostearate, PEG-7 hydrogenatedcastor oil, polyglyceryl-4 isostearate, acrylate/C₁₀₋₃₀-alkyl acrylatecrosspolymer, sorbitan isostearate, poloxamer 101, polyglyceryl-2dipolyhydroxy-stearate, polyglyceryl-3 diisostearate, polyglyceryl-4dipolyhydroxystearate, PEG-30 dipolyhydroxystearate, diisostearoylpolyglyceryl-3 diisostearate, glycol distearate, polyglyceryl-3dipolyhydroxystearate) or fatty acid esters of sulfuric acid orphosphoric acid (cetyl phosphate, trilaureth-4 phosphate, trioleth-8phosphate, stearyl phosphate, cetearyl sulfate etc.) can be used.

Further advantageous sprayable O/W emulsions for the purposes of thepresent invention are low-viscosity cosmetic or dermatologicalhydrodispersions which comprise at least one oil phase and at least onewater phase, where the preparation is stabilized by at least one gelformer and does not necessarily have to comprise emulsifiers, but maycomprise one or more emulsifiers.

Advantageous gel formers for such preparations are, for example,copolymers of C₁₀₋₃₀-alkyl acrylates and one or more monomers of acrylicacid, of methacrylic acid or esters thereof. The INCl name for suchcompounds is “Acrylates/C10-30 Alkyl Acrylate Crosspolymer”. ThePemulen® grades TR1, TR2 and TRZ from Goodrich (Noveon) are particularlyadvantageous.

Carbopols are also advantageous gel formers for such preparations.Carbopols are polymers of acrylic acid, in particular alsoacrylate-alkyl acrylate copolymers. Advantageous carbopols are, forexample, the grades 907, 910, 934, 940, 941, 951, 954, 980, 981, 1342,1382, 2984 and 5984, likewise the ETD grades 2020, 2050 and CarbopolUltrez 10. Further advantageous gel formers for such preparations arexanthan gum, cellulose derivatives and carob seed flour.

Possible (optional) emulsifiers which may be used are ethoxylated fattyalcohols or ethoxylated fatty acids (in particular PEG-100 stearate,ceteareth-20) and other nonionic surface-active substances.

The very low-viscosity to sprayable emulsions may also advantageously beW/O emulsions or water-in-silicone oil (W/S) emulsions. W/O or W/Semulsions which comprise

-   -   at least one silicone emulsifier (W/S) with a HLB value of ≦8 or        at least one W/O emulsifier with a HLB value of <7 and    -   at least one O/W emulsifier with a HLB value of >10 are        particularly advantageous.

Such preparations further comprise at least 20% by weight of lipids,where the lipid phase can also advantageously comprise silicone oils, oreven consist entirely of such oils.

The silicone emulsifier or emulsifiers can advantageously be chosen fromthe group of alkyl methicone copolyols or alkyldimethicone copolyols(e.g. dimethicone copolyols which are sold by Goldschmidt AG under thetrade names Abil® B 8842, Abil® B 8843, Abil® B8847, Abil® B 8851, Abil®B 8852, Abil® B 8863, Abil® B 8873 and Abil® B 88183, cetyl dimethiconecopolyol [Goldschmidt AG/Abil® EM 90], cyclomethicone dimethiconecopolyol [Goldschmidt AG/Abil® EM 97], lauryl methicone copolyol [DowCorning Ltd./Dow Corning® 5200 Formulation Aid], octyl dimethiconeethoxyglucoside [Wacker].

The W/O emulsifier or emulsifiers with a HLB value of <7 canadvantageously be chosen from the following group: sorbitan stearate,sorbitan oleate, lecithin, glyceryl lanolate, lanolin, hydrogenatedcastor oil, glyceryl isostearate, polyglyceryl-3 oleate, pentaerythritylisostearate, methylglucose dioleate, methylglucose dioleate in a mixturewith hydroxystearate and beeswax, PEG-7 hydrogenated castor oil,polyglyceryl-4 isostearate, hexyl laurate, acrylate/C₁₀₋₃₀-alkylacrylate crosspolymer, sorbitan isostearate, poloxamer 101,polyglyceryl-2 dipolyhydroxystearate, polyglyceryl-3 diisostearate,PEG-30 dipolyhydroxystearate, diisostearoyl polyglyceryl-3diisostearate, polyglyceryl-3 dipolyhydroxystearate, polyglyceryl-4dipolyhydroxystearate, polyglyceryl-3 dioleate.

The O/W emulsifier or emulsifiers with a HLB value of >10 canadvantageously be chosen from the following group: glyceryl stearate ina mixture with ceteareth-20, ceteareth-25, ceteareth-6 in a mixture withstearyl alcohol, cetylstearyl alcohol in a mixture with PEG-40 castoroil and sodium cetylstearyl sulfate, triceteareth-4 phosphate, glycerylstearate, sodium cetylstearyl sulfate, lecithin trilaureth-4 phosphate,laureth-4 phosphate, stearic acid, propylene glycol stearate SE, PEG-9stearate, PEG-20 stearate, PEG-30 stearate, PEG-40 stearate, PEG-100stearate, ceteth-2, ceteth-20, polysorbate-20, polysorbate-60,polysorbate-65, polysorbate-100, glyceryl stearate in a mixture withPEG-100 stearate, ceteareth-3, isostearyl glyceryl ether, cetylstearylalcohol in a mixture with sodium cetylstearyl sulfate, PEG-40 stearate,glycol distearate, PEG-22 dodecyl glycol copolymer, polyglyceryl-2 PEG-4stearate, ceteareth-12, ceteareth-20, ceteareth-30, methylglucosesesquistearate, steareth-10, PEG-20 stearate, steareth-21, steareth-20,isosteareth-20, PEG-45/dodecyl glycol copolymer, methoxy-PEG-22/dodecylglycol copolymer, glyceryl stearate SE, ceteth-20, PEG-20 methylglucosesesquistearate, glyceryl stearate citrate, cetyl phosphate, cetearylsulfate, sorbitan sesquioleate, triceteareth-4 phosphate, trilaureth-4phosphate, polyglyceryl methylglucose distearate, potassium cetylphosphate, isosteareth-10, polyglyceryl-2 sesquiisostearate, ceteth-10,isoceteth-20, glyceryl stearate in a mixture with ceteareth-20,ceteareth-12, cetylstearyl alcohol and cetyl palmitate, PEG-30 stearate,PEG-40 stearate, PEG-100 stearate.

Aqueous-alcoholic solutions are also advantageous. They can comprisefrom 0% by weight to 90% by weight of ethanol. Aqueous-alcoholicsolutions for the purposes of the present invention may advantageouslyalso comprise solubility promoters, such as, for example, PEG-40 orPEG-60 hydrogenated castor oil.

The preparations according to the invention can advantageously also beused as cosmetic or dermatological impregnation solutions with whichwater-insoluble substrates in particular—such as, for example, woven ornonwoven wipes—are moistened. Impregnation solutions of this type arepreferably of low viscosity, in particular sprayable (such as, forexample, PIT emulsions, hydrodispersions, W/O emulsions, oils, aqueoussolutions etc.) and preferably have a viscosity of less than 2000 mPa·s,in particular less than 1500 mPa·s (measuring device: Haake ViskotesterVT-02 at 25° C.). They can be used to obtain, for example, cosmeticsunscreen wipes, care wipes and the like, which represent thecombination of a soft, water-insoluble material with the low viscositycosmetic and dermatological impregnation solution.

Mousses

Also particularly advantageous for the purposes of the present inventionare self-foaming, foam-like, after-foaming or foamable cosmetic anddermatological preparations.

“Self-foaming”, “foam-like”, “after-foaming” and “foamable” preparationsare understood as meaning preparations from which foams can in principlebe produced by introducing one or more gases—whether during thepreparation process, whether upon use by the consumer or in another way.In such foams, the gas bubbles are (randomly) distributed in one (ormore) liquid phase(s), where the (foamed) preparations do notnecessarily have to have the appearance of a foam in macroscopic terms.Cosmetic or dermatological preparations (foamed) according to theinvention (referred to below for the sake of simplicity also as foams)may, for example, be macroscopically visibly dispersed systems of gasesdispersed in liquids. The foam character may, however, for example alsoonly be visible under a (light) microscope. Moreover, foams according tothe invention—particularly when the gas bubbles are too small to be seenunder a light microscope—are also evident from the considerable volumeincrease of the system.

For the purposes of the present invention, such preparationsadvantageously comprise an emulsifier system which consists of

-   A. at least one emulsifier chosen from the group of completely    neutralized, partially neutralized or unneutralized, branched or    unbranched, saturated or unsaturated fatty acids with a chain length    of from 10 to 40 carbon atoms,-   B. at least one emulsifier chosen from the group of polyethoxylated    fatty acid esters with a chain length of from 10 to 40 carbon atoms    and with a degree of ethoxylation of from 5 to 100 and-   C. at least one coemulsifier C chosen from the group of saturated or    unsaturated, branched or unbranched fatty alcohols with a chain    length of from 10 to 40 carbon atoms.

The emulsifier or emulsifiers A are preferably chosen from the group offatty acids, which are completely or partially neutralized withcustomary alkalis (such as, for example, sodium hydroxide or potassiumhydroxide, sodium carbonate or potassium carbonate, and mono- ortriethanolamine). Stearic acid and stearates, isostearic acid andisostearates, palmitic acid and palmitates, and myristic acid andmyristates, for example, are particularly advantageous.

The emulsifier or emulsifiers B are preferably chosen from the followinggroup: PEG-9 stearate, PEG-8 distearate, PEG-20 stearate, PEG-8stearate, PEG-8 oleate, PEG-25 glyceryl trioleate, PEG-40 sorbitanlanolate, PEG-15 glyceryl ricinoleate, PEG-20 glyceryl stearate, PEG-20glyceryl isostearate, PEG-20 glyceryl oleate, PEG-20 stearate, PEG-20methylglucose sesquistearate, PEG-30 glyceryl isostearate, PEG-20glyceryl laurate, PEG-30 stearate, PEG-30 glyceryl stearate, PEG-40stearate, PEG-30 glyceryl laurate, PEG-50 stearate, PEG-100 stearate,PEG-150 laurate. Polyethoxylated stearic esters, for example, areparticularly advantageous.

According to the invention, the coemulsifier or the coemulsifiers C arepreferably chosen from the following group: behenyl alcohol (C₂₂H₄₅OH),cetearyl alcohol [a mixture of cetyl alcohol (C₁₆H₃₃OH) and stearylalcohol (C₁₈H₃₇OH)], lanolin alcohols (wool wax alcohols which are theunsaponifiable alcohol fraction of wool wax which is obtained followingsaponification of wool wax). Cetyl and cetylstearyl alcohol areparticularly preferred.

It is advantageous according to the invention to choose the weightratios of emulsifier A to emulsifier B to emulsifier C (A:B:C) as a:b:c,where a, b and c, independently of one another, may be rational numbersfrom 1 to 5, preferably from 1 to 3. A weight ratio of, for example,1:1:1 is particularly preferred.

For the purposes of the present invention, it is advantageous to choosethe total amount of the emulsifiers A and B and of coemulsifier C fromthe range from 2 to 20% by weight, advantageously from 5 to 15% byweight, in particular from 7 to 13% by weight, in each case based on thetotal weight of the formulation.

Pickering/Solids-Stabilized Emulsions

Also particularly advantageous for the purposes of the present inventionare cosmetic or dermatological preparations which have been stabilizedonly by very finely divided solids particles. Such “emulsifier-free”emulsions are also referred to as Pickering emulsions.

In Pickering emulsions, the solid material accumulates at the oil/waterinterface in the form of a layer, as a result of which coalescence ofthe disperse phases is prevented. Of essential importance here are, inparticular, the surface properties of the solids particles, which shouldexhibit both hydrophilic and also lipophilic properties.

The stabilizing solids particles can also advantageously be treated(“coated”) to repel water, the intention being to form or retain anamphiphilic character of these solids particles. The surface treatmentcan consist in providing the solids particles with a thin hydrophobic orhydrophilic coat by processes known per se.

The average particle diameter of the microfine solids particles used asstabilizer is preferably chosen to be less than 100 μm, particularlyadvantageously less than 50 μm. In this connection, it is essentiallyunimportant in what form (platelets, rods, spheres, etc.) ormodifications the solids particles used are present.

The microfine solids particles are preferably chosen from the group ofamphiphilic metal oxide pigments. In particular,

-   -   titanium dioxides (coated and uncoated): e.g. Eusolex T-2000        from Merck, titanium dioxide MT-100 Z from Tayca Corporation    -   zinc oxides, e.g. Z-Cote and Z-Cote HP1 from BASF AG, MZ-300,        MZ-500 and MZ-505M from Tayca Corporation    -   iron oxides        are advantageous.

Furthermore, it is advantageous when the microfine solids particles arechosen from the following group: boron nitrides, starch derivatives(tapioca starch, sodium corn starch octynyl succinate etc.), talc, latexparticles.

It is advantageous according to the invention when the solids-stabilizedemulsions comprise significantly less than 0.5% by weight of one or moreemulsifiers or are even entirely emulsifier-free.

Sticks

Also advantageous for the purposes of the invention are preparations inthe form of sticks. Viewed technically, most stick formulations areanhydrous fatty mixtures of solid or semisolid waxes and liquid oils,where highly purified paraffin oils and paraffin waxes are the stickbase.

Customary bases for stick preparations are, for example, liquid oils(such as, for example, paraffin oils, castor oil, isopropyl myristate,C₁₂₋₁₅ alkyl benzoate), semisolid constituents (e.g. vaseline, lanolin),solid constituents (e.g. beeswax, ceresin and microcrystalline waxes andozokerite) or high-melting waxes (e.g. carnauba wax, candelilla wax).Water-containing stick preparations are also known per se, it beingpossible for these also to be present in the form of W/O emulsions.

The cosmetic or dermatological light-protective formulations accordingto the invention can have the customary composition and be used forcosmetic or dermatological light-protective, and also for the treatment,care and cleansing of the skin or of the hair and as a make-up productin decorative cosmetics.

Depending on their formulation, cosmetic or topical dermatologicalcompositions for the purposes of the present invention can, for example,be used as skin protection cream, cleansing milk, day or night creametc. It is optionally possible and advantageous to use the compositionsaccording to the invention as a base for pharmaceutical formulations.

For use, the cosmetic and dermatological preparations are applied to theskin or the hair in an adequate amount in the manner customary forcosmetics.

The cosmetic and dermatological preparations according to the inventioncan comprise cosmetic auxiliaries as are customarily used in suchpreparations, e.g. preservatives, preservative aids, complexing agents,bactericides, perfumes, substances for preventing or increasing foaming,dyes, pigments which have a coloring action, thickeners, moisturizing orhumectant substances, fillers which improve the feel on the skin, fats,oils, waxes or other customary constituents of a cosmetic ordermatological formulation, such as alcohols, polyols, polymers, foamstabilizers, electrolytes, organic solvents or silicone derivatives.

Advantageous preservatives for the purposes of the present inventionare, for example, formaldehyde donors (such as, for example, DMDMhydantoin, which is available, for example, under the trade nameGlydant™ from Lonza), iodopropyl butylcarbamates (e.g. those availableunder the trade names Glycacil-L, Glycacil-S from Lonza, or Dekaben LMBfrom Jan Dekker), parabens (i.e. alkyl p-hydroxybenzoates, such asmethyl-, ethyl-, propyl- or butylparaben), phenoxyethanol, ethanol,benzoic acid and the like. In addition, the preservative systemaccording to the invention also usually advantageously comprisespreservative aids, such as, for example, octoxyglycerol, glycine soyaetc.

Advantageous complexing agents for the purposes of the present inventionare, for example, EDTA, [S,S]-ethylenediamine disuccinate (EDDS), whichis available, for example, under the trade name Octaquest from Octel,pentasodium ethylenediamine tetramethylenephosphonate, which isavailable, for example, under the trade name Dequest 2046 from Monsantoand iminodisuccinic acid, which is available, inter alia, from Bayer AGunder the trade names Iminodisuccinate VP OC 370 (about 30% strengthsolution) and Baypure CX 100 solid.

Particularly advantageous preparations are also obtained whenantioxidants are used as additives or active ingredients. According tothe invention, the preparations advantageously comprise one or moreantioxidants. Favorable, but nevertheless optional, antioxidants whichmay be used are all antioxidants customary or suitable for cosmetic ordermatological applications.

For the purposes of the present invention, water-soluble antioxidantsmay be used particularly advantageously, such as, for example, vitamins,e.g. ascorbic acid and derivatives thereof.

Preferred antioxidants are also vitamin E and derivatives thereof, andvitamin A and derivatives thereof.

The amount of antioxidants (one or more compounds) in the preparationsis preferably 0.001 to 30% by weight, particularly preferably 0.05 to20% by weight, in particular 0.1 to 10% by weight, based on the totalweight of the preparation.

If vitamin E and derivatives thereof are the antioxidant or theantioxidants, it is advantageous to choose their respectiveconcentrations from the range from 0.001 to 10% by weight, based on thetotal weight of the formulation.

If vitamin A or vitamin A derivatives, or carotenes or derivativesthereof are the antioxidant or the antioxidants, it is advantageous tochoose their respective concentrations from the range from 0.001 to 10%by weight, based on the total weight of the formulation.

It is particularly advantageous when the cosmetic preparations accordingto the present invention comprise cosmetic or dermatological activeingredients, preferred active ingredients being antioxidants which canprotect the skin against oxidative stress.

Further advantageous active ingredients for the purposes of the presentinvention are natural active ingredients or derivatives thereof, suchas, for example, α-lipoic acid, phytoene, D-biotin, coenzyme Q10,α-glucosylrutin, carnitine, carnosine, natural or syntheticisoflavonoids, creatine, taurine or β-alanine, and8-hexadecene-1,16-dicarboxylic acid (dioic acid, CAS number 20701-68-2;provisional INCl name Octadecenedioic acid).

Formulations according to the invention which comprise, for example,known antiwrinkle active ingredients, such as flavone glycosides (inparticular α-glycosylrutin), coenzyme Q10, vitamin E or derivatives andthe like are particularly advantageously suitable for the prophylaxisand treatment of cosmetic or dermatological changes in the skin, asarise, for example, during the skin aging (such as, for example,dryness, roughness and formation of dryness wrinkles, itching, reducedrefatting (e.g. after washing), visible vascular dilations(telangiectases, cuperosis), flaccidity and formation of wrinkles andlines, local hyperpigmentation, hypopigmentation and incorrectpigmentation (e.g. age spots), increased susceptibility to mechanicalstress (e.g. cracking) and the like). In addition, they areadvantageously suitable to counter the appearance of dry or rough skin.

The water phase of the preparations according to the invention canadvantageously comprise customary cosmetic auxiliaries, such as, forexample, alcohols, in particular those of low carbon number, preferablyethanol or isopropanol, diols or polyols of low carbon number, andethers thereof, preferably propylene glycol, glycerol, butylene glycol,ethylene glycol, ethylene glycol monoethyl or monobutyl ether, propyleneglycol monomethyl, monoethyl or monobutyl ether, diethylene glycolmonomethyl or monoethyl ether and analogous products, polymers, foamstabilizers, electrolytes, and in particular one or more thickeners,which may advantageously be chosen from the group consisting of silicondioxide, aluminum silicates or polysaccharides or derivatives thereof,e.g. hyaluronic acid, xanthan gum, hydroxypropylmethylcellulose,particularly advantageously from the group of polyacrylates, preferablya polyacrylate from the group of so-called Carbopols [from Bf.Goodrich], for example carbopol grades 980, 981, 1382, 2984, 5984, ETD2020, ETD 2050, Ultrez 10, in each case individually or in combination.

In addition, the preparations according to the invention canadvantageously also comprise self-tanning substances, such as, forexample, dihydroxyacetone or melanin derivatives in concentrations offrom 1% by weight to 8% by weight, based on the total weight of thepreparation.

In addition, the preparations according to the invention canadvantageously also comprise repellents for protection against flies,ticks and spiders and the like. For example,N,N-diethyl-3-methylbenzamide (trade name: Meta-delphene, “DEET”),dimethyl phthalate (trade name: Palatinol M, DMP) and in particularethyl 3-(N-n-butyl-N-acetylamino)propionate (available under the tradename Insekt Repellent® 3535 from Merck). The repellents can either beused individually or in combination.

Moisturizers is the term used to refer to substances or mixtures ofsubstances which impart to cosmetic or dermatological preparations theproperty, following application or distribution on the surface of theskin, of reducing moisture release by the horny layer (also calledtrans-epidermal water loss (TEWL)) or of positively influencinghydration of the horny layer.

Advantageous moisturizers for the purposes of the present invention are,for example, glycerol, lactic acid, and lactates, in particular sodiumlactate, butylene glycol, propylene glycol, biosaccharide gum-1, glycinesoya, ethylhexyloxyglycerol, pyrrolidone-carboxylic acid and urea. Inaddition, it is particularly advantageous to use polymeric moisturizersfrom the group of water-soluble or water-swellable or water-gelablepolysaccharides. Hyaluronic acid, chitosan, and a fucose-richpolysaccharide, which is filed in the Chemical Abstracts under theregistry number 178463-23-5 and which is available, for example, underthe name Fucogel® 1000 by SOLABIA S.A., for example, are particularlyadvantageous. Moisturizers can advantageously also be used asanti-wrinkle active ingredients for the prophylaxis and treatment ofcosmetic or dermatological changes in the skin, as arise, for example,during skin aging.

The cosmetic or dermatological preparations according to the inventioncan also advantageously, but not necessarily, comprise fillers, which,for example, further improve the sensory and cosmetic properties of theformulations and, for example, bring about or enhance a velvety or silkyfeel on the skin. Advantageous fillers for the purposes of the presentinvention are starch and starch derivatives (such as, for example,tapioca starch, distarch phosphate, aluminum or sodium starchoctenylsuccinate and the like), pigments which have neither a primarilyUV filter effect nor a coloring effect (such as, for example, boronnitride etc.), and Aerosils® (CAS No. 7631-86-9).

The oil phase of the formulations according to the invention isadvantageously chosen from the group of polar oils, for example from thegroup of lecithins and of fatty acid triglycerides, namely thetriglycerol esters of saturated or unsaturated, branched or unbranchedalkanecarboxylic acids with a chain length of from 8 to 24, inparticular 12 to 18, carbon atoms. The fatty acid triglycerides can, forexample, advantageously be chosen from the group of synthetic,semisynthetic and natural oils, such as, for example, cocoglyceride,olive oil, sunflower oil, soybean oil, peanut oil, rapeseed oil, almondoil, palm oil, coconut oil, castor oil, wheatgerm oil, grapeseed oil,thistle oil, evening primrose oil, macadamia nut oil and the like.

Also advantageous according to the invention are, for example, naturalwaxes of animal and vegetable origin, such as, for example, beeswax andother insect waxes, and berry wax, shea butter and lanolin (wool wax).

For the purposes of the present invention, further advantageous polaroil components may also be chosen from the group of esters of saturatedor unsaturated, branched or unbranched alkanecarboxylic acids with achain length of from 3 to 30 carbon atoms and saturated or unsaturated,branched or unbranched alcohols with a chain length of from 3 to 30carbon atoms, and from the group of esters of aromatic carboxylic acidsand saturated or unsaturated, branched or unbranched alcohols with achain length of from 3 to 30 carbon atoms. Such ester oils can thenadvantageously be chosen from the group consisting of octyl palmitate,octyl cocoate, octyl isostearate, octyldodecyl myristate,octyldodecanol, cetearyl isononanoate, isopropyl myristate, isopropylpalmitate, isopropyl stearate, isopropyl oleate, n-butyl stearate,n-hexyl laurate, n-decyl oleate, isooctyl stearate, isononyl stearate,isononyl isononanoate, 2-ethylhexyl palmitate, 2-ethylhexyl laurate,2-hexyldecyl stearate, 2-octyldodecyl palmitate, stearyl heptanoate,oleyl oleate, oleyl erucate, erucyl oleate, erucyl erucate, tridecylstearate, tridecyl trimellitate, and synthetic, semisynthetic andnatural mixtures of such esters, such as, for example, jojoba oil.

In addition, the oil phase can advantageously be chosen from the groupof dialkyl ethers and dialkyl carbonates, advantageous examples beingdicaprylyl ether (Cetiol OE) and dicaprylyl carbonate, for example thatavailable under the trade name Cetiol CC from Cognis.

It is also preferred that the oil component or components from the groupconsisting of isoeicosane, neopentyl glycol diheptanoate, propyleneglycol dicaprylate/dicaprate, caprylic/capric/diglyceryl succinate,butylene glycol dicaprylate/dicaprate, C₁₂₋₁₃-alkyl lactate,di-C₁₂₋₁₃-alkyl tartrate, triisostearin, dipentaerythritylhexacaprylate/hexacaprate, propylene glycol monoisostearate,tricaprylin, dimethyl isosorbide. It is particularly advantageous if theoil phase of the formulations according to the invention has a contentof C₁₂₋₁₅-alkyl benzoate or consists entirely of this.

Advantageous oil components are also, for example, butyloctyl salicylate(for example that available under the trade name Hallbrite BHB from CPHall), hexadecyl benzoate and butyloctyl benzoate and mixtures thereof(Hallstar AB) and diethylhexyl naphthalate (Hallbrite TQ or Corapan TQfrom H&R).

Any mixtures of such oil and wax components are also be usedadvantageously for the purposes of the present invention.

In addition, the oil phase can likewise advantageously also comprisenonpolar oils, for example those which are chosen from the group ofbranched and unbranched hydrocarbons and hydrocarbon waxes, inparticular mineral oil, vaseline (petrolatum), paraffin oil, squalaneand squalene, polyolefins, hydrogenated polyisobutenes andisohexadecane. Among the polyolefins, polydecenes are the preferredsubstances.

The oil phase can advantageously also have a content of cyclic or linearsilicone oils or consist entirely of such oils, although it is preferredto use an additional content of other oil phase components apart fromthe silicone oil or the silicone oils.

Silicone oils are high molecular weight synthetic polymeric compounds inwhich silicon atoms are joined in a chain-like or reticular manner viaoxygen atoms and the remaining valences of the silicon are saturated byhydrocarbon radicals (in most cases methyl, less often ethyl, propyl,phenyl groups etc.). Systematically, the silicone oils are referred toas polyorganosiloxanes. The methyl-substituted polyorganosiloxanes,which are the most important compounds of this group in terms of amountand are characterized by the following structural formula

are also referred to as polydimethylsiloxane or Dimethicone (INCl).Dimethicones have various chain lengths and various molecular weights.

Particularly advantageous polyorganosiloxanes for the purposes of thepresent invention are, for example, dimethylpolysiloxanes[poly(dimethylsiloxane)], which are available, for example, under thetrade names Abil 10 to 10 000 from Th. Goldschmidt. Also advantageousare phenylmethylpolysiloxanes (INCl: Phenyl Dimethicone, PhenylTrimethicone), cyclic silicones (octamethylcyclotetrasiloxane anddecamethylcyclopentasiloxane), which are also referred to in accordancewith INCl as Cyclomethicone, amino-modified silicones (INCl:Amodimethicone) and silicone waxes, e.g. polysiloxane-polyalkylenecopolymers (INCl: Stearyl Dimethicone and Cetyl Dimethicone) anddialkoxydimethylpolysiloxanes (Stearoxy Dimethicone and Behenoxy StearylDimethicone), which are available as various Abil wax grades from Th.Goldschmidt. However, other silicone oils can also be usedadvantageously for the purposes of the present invention, for examplecetyl dimethicone, hexamethylcyclotrisiloxane, polydimethylsiloxane,poly(methylphenylsiloxane).

The preparations according to the invention can also advantageouslycomprise one or more substances from the following group of siloxaneelastomers, for example in order to increase the water resistance or thelight-protective factor of the products:

-   (a) siloxane elastomers which contain the units R₂SiO and RSiO_(1.5)    or R₃SiO_(0.5) or SiO₂,    -   where the individual radicals R, in each case independently of        one another, are hydrogen, C₁₋₂₄-alkyl (such as, for example,        methyl, ethyl, propyl) or aryl (such as, for example, phenyl or        tolyl), alkenyl (such as, for example, vinyl), and the weight        ratio of the units R₂SiO to RSiO_(1.5) is chosen from the range        from 1:1 to 30:1;-   (b) siloxane elastomers which are insoluble and swellable in    silicone oil and which are obtainable by the addition reaction of an    organopolysiloxane (1) which contains silicon-bonded hydrogen with    an organopolysiloxane (2) which contains unsaturated aliphatic    groups,    -   where the quantitative amounts used are chosen such that the        amount of hydrogen in the organopolysiloxane (1) or in the        unsaturated aliphatic groups of the organopolysiloxane (2)        -   is in the range from 1 to 20 mol % when the            organopolysiloxane is noncyclic and        -   is in the range from 1 to 50 mol % when the            organopolysiloxane is cyclic.

For the purposes of the present invention, the siloxane elastomer orelastomers are advantageously present in the form of spherical powdersor in the form of gels.

Siloxane elastomers present in the form of spherical powders which areadvantageous according to the invention are those with the INCl nameDimethiconeNinyl Dimethicone Crosspolymer, for example that availablefrom DOW CORNING under the trade names DOW CORNING 9506 Powder.

It is particularly preferred when the siloxane elastomer is used incombination with oils from hydrocarbons of animal or vegetable origin,synthetic oils, synthetic esters, synthetic ethers or mixtures thereof.

It is very particularly preferred when the siloxane elastomer is used incombination with unbranched silicone oils which are liquid or pasty atroom temperature or cyclic silicone oils or mixtures thereof.Organopolysiloxane elastomers with the INCl nameDimethicone/Polysilicone-11, very particularly the Gransil gradesobtainable from Grant Industries Inc. GCM, GCM-5, DMG-6, CSE gel,PM-gel, LTX, ININ gel, AM-18 gel and DMCM-5 are particularlyadvantageous.

It is very extremely preferred when the siloxane elastomer is used inthe form of a gel of siloxane elastomer and a lipid phase where thecontent of the siloxane elastomer in the gel is 1 to 80% by weight,preferably 0.1 to 60% by weight, in each case based on the total weightof the gel.

It is advantageous for the purposes of the present invention to choosethe total amount of the siloxane elastomers (active content) from therange from 0.01 to 10% by weight, advantageously from 0.1 to 5% byweight, in each case based on the total weight of the formulation.

The cosmetic and dermatological preparations according to the inventioncan comprise dyes or color pigments, particularly when they are in theform of decorative cosmetics. The dyes and color pigments can be chosenfrom the corresponding positive list in the Cosmetics Directive or theEC list of cosmetic colorants. In most cases, they are identical to dyesapproved for foods. Advantageous color pigments are, for example,titanium dioxide, mica, iron oxides (e.g. Fe₂O₃, Fe₃O₄, FeO(OH)) and tinoxide. Advantageous dyes are, for example, carmine, Prussian blue,chromium oxide green, ultramarine blue and manganese violet. It isparticularly advantageous to choose the dyes or the color pigments fromthe Rowe Colour Index, 3^(rd) Edition, Society of Dyers and Colourists,Bradford, England, 1971.

If the formulations according to the invention are in the form ofproducts which are used on the face, it is favorable to choose one ormore substances from the following group as the dye:2,4-dihydroxyazobenzene,1-(2′-chloro-4′-nitro-1′-phenylazo)-2-hydroxynaphthalene, Ceres red,2-(sulfo-1-naphthylazo)-1-naphthol-4-sulfonic acid, calcium salt of2-hydroxy-1,2′-azonaphthalene-1′-sulfonic acid, calcium and barium saltsof 1-(2-sulfo4-methyl-1-phenylazo)-2-naphthylcarboxylic acid, calciumsalt of 1-(2-sulfo-1-naphthylazo)-2-hydroxynaphthalene-3-carboxylicacid, aluminum salt of 1-(4-sulfo-1-phenylazo)-2-naphthyl-6-sulfonicacid, aluminum salt of1-(4-sulfo-1-naphthylazo)-2-naphthyl-3,6-disulfonic acid,1-(4-sulfo-1-naphthylazo)-2-naphthol-6,8-disulfonic acid, aluminum saltof4-(4-sulfo-1-phenylazo)-1-(4-sulfophenyl)-5-hydroxypyrazolone-3-carboxylicacid, aluminum and zirconium salts of 4,5-dibromofluorescein, aluminumand zirconium salts of 2,4,5,7-tetrabromofluorescein,3′,4′,5′,6′-tetrachloro-2,4,5,7-tetrabromofluorescein and its aluminumsalt, aluminum salt of 2,4,5,7-tetraiodofluorescein, aluminum salt ofquinophthalonedisulfonic acid, aluminum salt of indigodisulfonic acid,red and black iron oxide (CIN: 77 491 (red) and 77 499 (black)), ironoxide hydrate (CIN: 77 492), manganese ammonium diphosphate and titaniumdioxide.

Also advantageous are oil-soluble natural dyes, such as, for example,paprika extracts, β-carotene or cochineal.

Also advantageous for the purposes of the present invention areformulations with a content of pearlescent pigments. Preference is givenin particular to the types of pearlescent pigments listed below:

-   1. Natural pearlescent pigments, such as, for example,    -   “pearlessence” (guanine/hypoxanthin mixed crystals from fish        scales) and    -   “mother-of-pearl” (ground mussel shells)-   2. Monocrystalline pearlescent pigments, such as, for example,    bismuth oxychloride (BiOCl)-   3. Layer-substrate pigments: e.g. mica/metal oxide

Bases for pearlescent pigments are, for example, pulverulent pigments orcastor oil dispersions of bismuth oxychloride or titanium dioxide, andbismuth oxychloride or titanium dioxide on mica. The luster pigmentlisted under CIN 77163, for example, is particularly advantageous.

Also advantageous are, for example, the following types of pearlescentpigments based on mica/metal oxide:

Group Coating/layer thickness Color Silver-white pearlescent TiO₂: 40–60nm Silver pigments Interference pigments TiO₂: 60–80 nm Yellow TiO₂:80–100 nm Red TiO₂: 100–140 nm Blue TiO₂: 120–160 nm Green Color lusterpigments Fe₂O₃ Bronze Fe₂O₃ Copper Fe₂O₃ Red Fe₂O₃ Red-violet Fe₂O₃Red-green Fe₂O₃ Black Combination pigments TiO₂/Fe₂O₃ Gold shadesTiO₂/Cr₂O₃ Green TiO₂/Prussian blue Deep blue TiO₂/carmine Red

Particular preference is given, for example, to the pearlescent pigmentsobtainable from Merck under the trade names Timiron, Colorona orDichrona.

The list of given pearlescent pigments is not of course intended to belimiting. Pearlescent pigments which are advantageous for the purposesof the present invention are obtainable by numerous methods known perse. For example, other substrates apart from mica can be coated withfurther metal oxides, such as, for example, silica and the like. SiO₂particles coated with, for example, TiO₂ and Fe₂O₃ (“ronaspheres”),which are sold by Merck and are particularly suitable for the opticalreduction of fine lines, are suitable.

It can, moreover, be advantageous to dispense completely with asubstrate such as mica. Particular preference is given to ironpearlescent pigments prepared without the use of mica. Such pigments areobtainable, for example, under the trade name Sicopearl Kupfer 1000 fromBASF.

In addition, also particularly advantageous are effect pigments whichare obtainable under the trade name Metasomes Standard/Glitter invarious colors (yellow, red, green, blue) from Flora Tech. The glitterparticles are present here in mixtures with various auxiliaries and dyes(such as, for example, the dyes with the Colour Index (Cl) numbers19140, 77007, 77289, 77491).

The dyes and pigments may be present either individually or in amixture, and can be mutually coated with one another, different coatingthicknesses generally giving rise to different color effects. The totalamount of dyes and color-imparting pigments is advantageously chosenfrom the range from, for example, 0.1% by weight to 30% by weight,preferably from 0.5 to 15% by weight, in particular from 1.0 to 10% byweight, in each case based on the total weight of the preparations.

For the purposes of the present invention, it is also advantageous toprovide cosmetic and dermatological preparations whose main purpose isnot protection against sunlight, but which nevertheless have a contentof further UV protection substances. Thus, for example, UV-A and/or UV-Bfilter substances are usually incorporated into daycreams or make-upproducts. UV protection substances, like antioxidants and, if desired,preservatives, also constitute effective protection of the preparationsthemselves against spoilage. Also favorable are cosmetic anddermatological preparations in the form of a sunscreen.

Accordingly, for the purposes of the present invention, the preparationspreferably additionally comprise at least one further UV-A, UV-B, orbroadband filter substance. The formulations can, but do notnecessarily, optionally comprise one or more organic or inorganicpigments as UV filter substances, which may be present in the waterphase or the oil phase.

In addition, the preparations according to the invention can alsoadvantageously be in the form of so-called oil-free cosmetic ordermatological emulsions, which comprise a water phase and at least oneUV filter substance which is liquid at room temperature as a furtherphase.

Particularly advantageous UV filter substances liquid at roomtemperature are, for the purposes of the present invention, homomenthylsalicylate (INCl: Homosalate), 2-ethylhexyl 2-cyano-3,3-diphenylacrylate(INCl: Octocrylene), 2-ethylhexyl 2-hydroxybenzoate (2-ethylhexylsalicylate, octyl salicylate, INCl: Octyl Salicylate) and esters ofcinnamic acid, preferably 2-ethylhexyl 4-methoxycinnamate (INCl: OctylMethoxycinnamate) and isopentyl 4-methoxycinnamate (INCl: Isoamylp-Methoxy-cinnamate)3-(4-(2,2-bisethoxycarbonylvinyl)phenoxy)propenyl)methoxy-silane/dimethylsiloxanecopolymer, which is available, for example, under the trade name Parsol®SLX from Hoffmann La Roche.

Preferred inorganic pigments are metal oxides or other metal compoundswhich are insoluble or sparingly soluble in water, in particular oxidesof titanium (TiO₂), zinc (ZnO), iron (e.g. Fe₂O₃), zirconium (ZrO₂),silicon (SiO₂), manganese (e.g. MnO), aluminum (Al₂O₃), cerium (e.g.Ce₂O₃), mixed oxides of the corresponding metals, and mixtures of suchoxides, and also the sulfate of barium (BaSO₄).

For the purposes of the present invention, the pigments mayadvantageously also be used in the form of commercially available oilyor aqueous predispersions. Dispersion auxiliaries or solubilitypromoters may advantageously be added to these predispersions.

According to the invention, the pigments may advantageously besurface-treated (“coated”), the intention being to form or retain, forexample, a hydrophilic, amphiphilic or hydrophobic character. Thissurface treatment can consist in providing the pigments with a thinhydrophilic or hydrophobic inorganic or organic coat by methods knownper se. For the purposes of the present invention, the various surfacecoatings may also comprise water.

Inorganic surface coatings for the purposes of the present invention mayconsist of aluminum oxide (Al₂O₃), aluminum hydroxide Al(OH)₃, oraluminum oxide hydrate (also: alumina, CAS No.: 1333-84-2), sodiumhexametaphosphate (NaPO₃)₆, sodium metaphosphate (NaPO₃)_(n), silicondioxide (SiO₂) (also: silica, CAS No.: 7631-86-9), or iron oxide(Fe₂O₃). These inorganic surface coatings may be present on their own,in combination or in combination with organic coating materials.

Organic surface coatings for the purposes of the present invention mayconsist of vegetable or animal aluminum stearate, vegetable or animalstearic acid, lauric acid, dimethylpolysiloxane (also: Dimethicone),methylpolysiloxane (Methicone), simethicone (a mixture ofdimethylpolysiloxane with an average chain length of from 200 to 350dimethylsiloxane units and silica gel) or alginic acid. These organicsurface coatings may be present on their own, in combination or incombination with inorganic coating materials.

Zinc oxide particles and predispersions of zinc oxide particles whichare suitable according to the invention are obtainable under thefollowing trade names from the companies listed:

Trade name Coating Manufacturer Z-Cote HP1 2% Dimethicone BASF Z-Cote /BASF ZnO NDM 5% Dimethicone H&R MZ-303S 3% Methicone Tayca CorporationMZ-505S 5% Methicone Tayca Corporation

Suitable titanium dioxide particles and predispersions of titaniumdioxide particles are available under the following trade names from thecompanies listed:

Trade name Coating Manufacturer MT-100TV Aluminum hydroxide/stearicTayca Corporation acid MT-100Z Aluminum hydroxide/stearic TaycaCorporation acid Eusolex T-2000 Alumina/Simethicone Merck KgaA Titaniumdioxide Octyltrimethylsilane Degussa T805 (Uvinul TiO₂) Tioveil AQ 10PGAlumina/Silica Solaveil/Uniquema

Further advantageous pigments are latex particles. Latex particlesadvantageous according to the invention are those described in thefollowing specifications: U.S. Pat. No. 5,663,213 and EP 0 761 201.Particularly advantageous latex particles are those which are formedfrom water and styrene/acrylate copolymers and are available, forexample, under the trade name “Alliance SunSphere” from Rohm & Haas.

Advantageous UV-A filter substances for the purposes of the presentinvention are dibenzoylmethane derivatives, in particular4-(tert-butyl)-4′-methoxydibenzoyl-methane (CAS No. 70356-09-1), whichis sold by Givaudan under the name Parsol® 1789 and by Merck under thetrade name Eusolex® 9020.

Further advantageous UV-A filter substances for the purposes of thepresent invention are hydroxybenzophenones which are characterized bythe following structural formula:

in which

-   -   R¹ and R², independently of one another, are hydrogen,        C₁–C₂₀-alkyl, C₃–C₁₀-cycloalkyl or C₃–C₁₀-cycloalkenyl, where        the substituents R¹ and R², together with the nitrogen atom to        which they are bonded, can form a 5-membered or 6-membered ring        and    -   R³ is a C₁–C₂₀-alkyl radical.

A particularly advantageous hydroxybenzophenone for the purposes of thepresent invention is hexyl 2-(4′-diethylamino-2′-hydroxybenzoyl)benzoate(also: Aminobenzophenone), which is characterized by the followingstructure:

and is available under Uvinul A Plus from BASF.

Advantageous UV filter substances for the purposes of the presentinvention are also so-called broadband filters, i.e. filter substanceswhich absorb both UV-A and also UV-B radiation.

Advantageous broadband filters or UV-B filter substances are, forexample, triazine derivatives, such as, for example,

-   -   2,4-bis{[4-(2-ethylhexyloxy)-2-hydroxy]phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine        (INCl: BisEthylhexyloxyphenol Methoxyphenyl Triazine), which is        available under the trade name Tinosorb® S from CIBA-Chemikalien        GmbH;    -   dioctylbutylamidotriazone (INCl: Diethylhexyl Butamido        Triazone), which is available under the trade name UVASORB HEB        from Sigma 3V;    -   tris(2-ethylhexyl)        4,4′,4″-(1,3,5-triazine-2,4,6-triyltriimino)trisbenzoate, also:        2,4,6-tris[anilino(p-carbo-2′-ethyl-1′-hexyloxy)]-1,3,5-triazine        (INCl: Octyl Triazone), which is sold by BASF Aktiengesellschaft        under the trade name UVINUL® T 150.

An advantageous broadband filter for the purposes of the presentinvention is also2,2′-methylenebis(6-(2H-benzotriazol-2-yl)4-(1,1,3,3-tetramethylbutyl)phenol),which is available under the trade name Tinosorb® M fromCIBA-Chemikalien GmbH.

For the purposes of the present invention, an advantageous broadbandfilter is also2-(2H-benzotriazol-2-yl)4-methyl-6-[2-methyl-3-[1,3,3,3-tetramethyl-1-[(trimethyl-silyl)oxy]disiloxanyl]propyl]phenol(CAS No.: 155633-54-8) with the INCl name Drometrizole Trisiloxane.

The further UV filter substances may be oil-soluble. Advantageousoil-soluble filter substances are, for example:

-   -   3-benzylidenecamphor derivatives, preferably        3-(4-methylbenzylidene)camphor, 3-benzylidenecamphor;    -   4-aminobenzoic acid derivatives, preferably 2-ethylhexyl        4-(dimethyl-amino)benzoate, amyl 4-(dimethylamino)benzoate;    -   derivatives of benzophenone, preferably        2-hydroxy-4-methoxybenzophenone,        2-hydroxy4-methoxy-4′-methylbenzophenone,        2,2′-dihydroxy-4-methoxybenzophenone    -   and UV filters bonded to polymers.

Further advantageous UV filters are the salts of2-phenylbenzimidazole-5-sulfonic acid, such as its sodium, potassium orits triethanolammonium salt, and the sulfonic acid itself

with the INCl name Phenylbenzimidazole Sulfonic Acid (CAS No.27503-81-7), which is available, for example, under the trade nameEusolex 232 from Merck, or under Neo Heliopan Hydro from Haarmann &Reimer.

A further light-protective filter substance to be used advantageouslyaccording to the invention is ethylhexyl 2-cyano-3,3-diphenylacrylate(octocrylene), which is available from BASF under the name Uvinul® N 539T.

Besides the filter substance(s) according to the invention, particularlyadvantageous preparations for the purposes of the present inventionwhich are characterized by high or very high UV-A protection preferablyalso comprise further UV-A or broadband filters, in particulardibenzoylmethane derivatives [for example4-(tert-butyl)-4′-methoxydibenzoylmethane] or2,4-bis{[4-(2-ethylhexyloxy)-2-hydroxy]phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine,in each case individually or in any combinations with one another.

The list of given UV filters which can be used for the purposes of thepresent invention is not of course intended to be limiting.

The preparations according to the invention, advantageously comprise thesubstances which absorb UV radiation in the UV-A and/or UV-B region in atotal amount of, for example, from 0.1% by weight to 30% by weight,preferably from 0.5 to 20% by weight, in particular 1.0 to 15.0% byweight, in each case based on the total weight of the preparations, inorder to provide cosmetic preparations which protect the hair or theskin from the entire range of ultraviolet radiation.

In addition, it may in some instances be advantageous to incorporatefilm formers into the cosmetic or dermatological preparations accordingto the invention, for example in order to improve the water resistanceof the preparations, or to increase the UV protection performance (UV-Aand/or UV-B boosting). Both water-soluble or dispersible and alsofat-soluble film formers are suitable, in each case individually or incombination with one another.

Advantageous water-soluble or dispersible film formers are, for example,polyurethanes (e.g. the Avalure® grades from Goodrich), DimethiconeCopolyol Polyacrylate (Silsoft Surface® from the Witco Organa SiliconesGroup), PVPNA (VA=vinyl acetate) copolymer (Luviscol VA 64 Powder fromBASF), C₂₀₋₄₀ carboxylic acid with polyethylene (Performacid 350 fromNew Phase Technologies) etc.

Advantageous fat-soluble film formers are, for example, the film formersfrom the group of polymers based on polyvinylpyrrolidone (PVP)

Particular preference is given to copolymers of polyvinylpyrrolidone,for example the PVP hexadecene copolymer and the PVP eicosene copolymer,which are available under the trade names Antaron V216 and Antaron V220from GAF Chemicals Cooperation, and also Tricontayl PVP and the like.

The examples below are intended to illustrate the present inventionwithout limiting it. The numerical values in the examples arepercentages by weight, based on the total weight of the respectivepreparations.

EXAMPLES

1. O/W sunscreen emulsions 1 2 3 4 5 6 7 Glycerol monostearate SE 0.501.00 3.00 1.50 Glyceryl stearate citrate 2.00 1.00 2.00 2.50 Stearicacid 3.00 0.75 2.00 PEG-40 stearate 0.50 2.00 PEG-100 stearate 1.50Cetyl dimethicone copolyol 0.75 0.50 Cetyl phosphate 0.75 1.00 Stearylalcohol 3.00 2.00 0.50 Cetyl alcohol 2.50 1.00 0.50 2.00 UVASorb ® K2A1.00 2.50 3.00 4.00 1.50 5.00 1.00 Phenylbenzimidazolesulfonic acid 0.501.00 2.00 0.50 Disodium phenyl dibenzimidazoletetrasulfonate 2.50 1.002.00 1.50 1.00 Terephthalidenedicamphorsulfonic 1.00 0.50 0.50 acidButylmethoxydibenzoylmethane 2.00 1.00 Uvinul ® A Plus 1.00Bisethylhexyloxyphenol 1.50 2.50 methoxyphenyltriazineEthylhexyltriazone 2.00 2.00 4.00 2.00 Diethylhexylbutamidotriazone 2.00Ethylhexyl methoxycinnamate 3.50 10.00 Octocrylene 5.00 9.00 7.50 2.50Methylenebisbenztriazolyltetramethylbutylphenol 2.00 0.50 Homosalate2.00 Ethylhexyl salicylate 3.00 5.00 Drometrizoltrisiloxane 0.5 1.00Titanium dioxide T 805 1.50 1.00 0.50 Titanium dioxide MT-100Z 1.00 3.001.00 Zinc oxide NDM 1.50 3.00 C12–15 alkyl benzoate 2.50 7.00 5.00Dicaprylyl ether 3.50 2.00 Butylene glycol 5.00 dicaprylate/dicaprateDibutyl adipate 6.00 2.00 2.00 Dimethicone 0.50 1.00 2.00 Cyclomethicone2.00 4.50 0.50 Shea butter 2.00 0.50 PVP hexadecene copolymer 0.50 0.501.00 1.00 Performacid ® 350 0.75 Glycerol 3.00 7.50 7.50 5.00 2.50Xanthan gum 0.15 0.05 0.30 Sodium carbomer 0.20 0.10 0.20 Vitamin EAcetate 0.5 0.25 0.50 0.75 1.00 Alpha-glucosylrutin 0.25 0.20 0.25Fucogel ® 1000 1.50 5.00 DMDM hydantoin 0.60 0.40 0.20 Konkaben LMB ®0.18 0.20 0.15 Methylparaben 0.15 0.25 0.50 Phenoxyethanol 1.00 0.400.40 0.50 0.60 EDTA 0.20 0.35 0.50 0.02 0.03 Ethanol 2.00 1.50 3.00 5.001.00 Dihydroxy acetone 7.50 Perfume 0.20 0.20 0.30 0.40 Water ad ad adad ad ad ad 100 100 100 100 100 100 100

2. Foam-like O/W emulsions: Emulsion 1 Emulsion 2 % by wt. % by vol. %by wt. % by vol. Stearic acid 5.00 1.00 Cetyl alcohol 5.50 Cetylstearylalcohol 2.00 PEG-40 stearate 8.50 PEG-20 stearate 1.00 Caprylic/caprictriglycerides 4.00 2.00 C12–15 alkyl benzoate 10.00 15.50 Cyclomethicone4.00 Dimethicone 0.50 Octyl isostearate 5.00 Myristyl myristate 2.00Ceresine 1.50 Glycerol 3.00 UVASorb ® K2A 2.00 4.00Phenylbenzimidazolesulfonic acid 0.50 Disodium 2.00 1.50phenyldibenzimidazoletetra- sulfonate Terephthalidenedicamphorsulfonic0.50 acid Ethylhexyl methoxycinnamate 5.00 4.00Butylmethoxydibenzoylmethane 3.00 Ethylhexyltriazone 3.00 Octocrylene5.00 Titanium dioxide MT-100 TV 1.00 BHT 0.02 Na₂H₂EDTA 0.50 0.10Perfume, preservative, q.s. q.s. Dyes, etc. q.s. q.s. Potassiumhydroxide q.s. q.s. Water ad 100.00 ad 100.00 pH adjusted to 6.5–7.5 pHadjusted to 5.0–6.0 Emulsion 1 70 Emulsion 2 35 Gas (nitrogen) 30 Gas(helium) 65

Combining of the fatty/light-protective filter phase heated to 78° C.with the water/light-protective filter phase heated to 75° C.Homogenization using a toothed-wheel dispersing machine (rotor-statorprinciple) at 65° C. Stirring for 45 min in the Becomix with gassingwith helium at 1 bar with cooling to 30° C. Addition of the additives at30° C. (perfume). Homogenization by means of a toothed-wheel dispersingmachine (rotor-stator principle) at 23° C.

3. PIT emulsions (for use as impregnation solution, spray or aerosol) 12 3 4 5 6 7 8 Glycerol monostearate SE 0.50 2.00 3.00 5.00 0.50 4.00Glyceryl isostearate 3.50 4.00 2.00 Isoceteth-20 0.50 2.00 Ceteareth-125.00 1.00 3.50 Ceteareth-20 2.00 2.50 3.00 PEG-100 stearate 5.00 1.001.00 0.50 Cetyl alcohol 2.50 1.00 1.50 0.50 1.50 Cetyl palmitate 0.501.00 Cetyldimethicone copolyol 0.50 0.50 1.00 Polyglyceryl-2dipolyhydroxystearate 0.75 0.25 UVASorb ® K2A 1.50 2.00 2.00 3.00 2.503.00 1.00 3.50 Disodium phenyldibenzimidazoletetrasulfonate 2.00 1.001.00 2.00 Terephthalidenedicamphorsulfonic 0.50 1.00 acidPhenylbenzimidazolesulfonic 1.00 2.00 2.00 acid Uvinul ® A Plus 2.001.00 Bisethylhexyloxyphenol 0.50 2.00 1.00 0.75 methoxyphenyltriazineButylmethoxydibenzoylmethane 1.50 1.00 0.75 Drometrizoletrisiloxane 2.003.00 1.00 Ethylhexyl 8.00 4.50 5.00 10.00 methoxycinnamateDiethylhexylbutamidotriazone 2.00 2.00 1.50 Ethylhexyltriazone 2.00 4.002.00 1.50 3.00 Octocrylene 5.00 10.00 7.50 C12–15 alkyl benzoate 3.50Cocoglycerides 3.00 3.00 3.50 Dicaprylyl ether 4.00 2.00 Butylene glycol4.00 3.00 dicaprylate/dicaprate Dicaprylyl carbonate 5.00 6.00Phenyltrimethicone 2.00 2.00 PVP hexadecene copolymer 1.00 1.50 Glycerol10.0 5.00 7.50 10.00 Fucogel ® 1000 2.50 6.00 Tocopherol 1.00 0.75 0.501.00 Shea butter 2.00 3.50 0.50 Iodopropyl butylcarbamate 0.12 0.20 DMDMhydantoin 0.10 Methylparaben 0.50 0.25 0.45 Phenoxyethanol 0.50 0.401.00 1.00 Ethylhexyloxyglycerol 0.30 1.00 0.35 Ethanol 2.00 6.00 7.504.00 Trisodium EDTA 0.40 0.15 0.20 0.50 Perfume 0.20 0.20 0.20 0.45 0.20Water ad ad ad ad ad ad ad ad 100 100 100 100 100 100 100 100

4. Low viscosity to sprayable W/O emulsions (for use as impregnationsolution, spray or aerosol) 1 2 3 4 5 Cetyl dimethicone copolyol 4.002.50 3.00 Polyglyceryl-2 dipolyhydroxystearate 3.00 1.00 Isostearyldiglyceryl succinate 0.75 0.30 Lauryl methicone copolyol 2.00Polysorbate-65 2.00 1.50 PEG-100 stearate 1.20 0.70 Cetearyl sulfate0.25 1.00 Dimethicone 4.00 2.00 Cyclomethicone 12.00 20.00 30.00 15.00UVASorb ® K2A 2.00 1.50 3.00 0.50 5.00 Disodium 1.00 0.75 3.00phenyldibenzimidazoletetrasulfonate Terephthalidenedicamphorsulfonic0.50 1.00 acid Phenylbenzimidazolesulfonic acid 1.50 2.00 2.00 Uvinul ®A Plus 1.00 0.75 Bisethylhexyloxyphenol 1.50 2.00 0.50methoxyphenyltriazine Drometrizole trisiloxane 1.00 Ethylhexylmethoxycinnamate 3.00 4.00 10.00 Diethylhexylbutamidotriazone 1.00 6.50Ethylhexyltriazone 3.00 4.00 Titanium dioxide MT-100 TV 0.50 1.00 1.500.50 Zinc oxide Z-Cote HP1 2.00 4.00 Dicaprylyl carbonate 5.00 15.004.00 Dihexyl carbonate 10.00 C12–15 alkyl benzoate 7.00 10.00 Mineraloil 10.00 6.00 PVP hexadecene copolymer 0.75 0.40 Glycerol 5.00 7.00α-Glucosylrutin 0.15 EDTA 0.15 0.03 0.15 Glycine soya 0.75 1.50Magnesium sulfate 0.75 1.00 0.45 1.00 Sodium chloride 1.00 DMDMhydantoin 0.05 0.10 Phenoxyethanol 1.00 0.75 0.50 1.00 Ethanol 2.00 5.001.00 Dye 0.02 0.01 Perfume 0.30 0.45 0.35 0.15 Water ad 100 ad 100 ad100 ad 100 ad 100

5. W/O sunscreen emulsions (creams and lotions) 1 2 3 4 5Cetyldimethicone copolyol 4.00 Polyglyceryl-2 5.00 4.50 4.50dipolyhydroxystearate PEG-30 dipolyhydroxystearate 5.00 2.00 UVASorb ®K2A 3.50 2.00 1.50 4.00 0.50 Disodiumphenyldibenzimidazoletetrasulfonate1.00 1.00 1.00 2.00 Terephthalidenedicamphorsulfonic 0.75 acidPhenylbenzimidazolesulfonic acid 4.00 2.00 0.50 Uvinul ® A Plus 2.001.00 Methylenebisbenzotriazolyltetramethylbutylphenol 2.00 0.50Bisethylhexyloxyphenol 2.00 2.00 2.50 methoxyphenyltriazineButylmethoxydibenzoylmethane 2.00 1.00 Ethylhexyl methoxycinnamate 8.005.00 4.00 Diethylhexylbutamidotriazone 3.00 1.00 3.00 Ethylhexyltriazone3.00 4.00 Parsol ® SLX 5.00 Octocrylene 7.00 8.00 2.50 Titanium dioxideUvinul ® T 805 2.00 1.00 Titanium dioxide MT-100 Z 3.00 2.00 Zinc oxideZ-Cote ® HP1 2.50 6.00 Mineral oil 10.0 8.00 Cocoglycerides 4.00 6.50C12–15 alkyl benzoates 9.00 Dicaprylyl ether 10.00 7.00 Butylene glycol2.00 8.00 4.00 dicaprylate/dicaprate Cyclomethicone 2.00 2.00 PVPhexadecene copolymer 0.50 1.50 1.00 Baypure CX 100 ® 0.45 0.75 0.25Trisodium EDTA 1.00 0.35 Ethylhexyloxyglycerol 0.30 1.00 0.50 Glycerol3.00 7.50 7.50 2.50 Butylene glycol 10.00 6.50 Glycine soya 1.00 1.50MgSO₄ 1.00 0.50 0.50 MgCl₂ 1.00 0.70 Vitamin E 0.50 0.25 1.00 DMDMhydantoin 0.60 0.20 Methylparaben 0.50 0.15 Phenoxyethanol 0.50 0.401.00 0.60 Ethanol 3.00 4.50 1.00 Perfume 0.20 0.20 0.20 Water ad 100 ad100 ad 100 ad 100 ad 100

6. Hydrodispersions (for use as lotion, impregnation solution or spray)1 2 3 4 5 Ceteareth-20 1.00 0.5 Cetyl alcohol 1.00 Sodium carbomer 0.200.30 Acrylates/C10–30 alkyl acrylate 0.40 0.10 0.10 crosspolymer Xanthangum 0.50 0.30 0.15 0.50 Dimethicone/vinyldimethicone 5.00 3.00crosspolymer UVASorb ® K2A 2.00 1.50 4.00 3.50 0.50Disodiumphenyldibenzimidazoletetrasulfonate 4.00 1.00 0.50 2.00Terephthalidenedicamphorsulfonic 0.20 0.50 acidPhenylbenzimidazolsulfonic acid 1.00 2.00 Uvinul ® A Plus 3.00 0.50Ethylhexyl methoxycinnamate 5.00 8.00 Bisethylhexyloxyphenolmethoxyphenyltriazine 1.50 2.00 1.00 Butylmethoxydibenzoylmethane 1.000.50 0.50 Diethylhexylbutamidotriazone 2.00 1.00 1.00Methylenebis-benzotriazolyltetramethylbutylphenol 3.00Ethylhexyltriazone 4.00 3.00 4.00 Octocrylene 4.00 10.00 2.50 Titaniumdioxide T805 ® 0.50 2.00 3.00 1.00 Zinc oxide Z-Cote ® 2.00 4.00 C12–15alkyl benzoates 2.00 2.50 Butylene glycol dicaprylate/dicaprate 4.006.00 Dicaprylyl carbonate 2.00 Dimethicone 0.50 12.50 4.50 7.00Cyclomethicone 10.00 2.00 2.50 10.00 Shea butter 2.00 PVP hexadecenecopolymer 0.50 0.50 1.00 Ethylhexyloxyglycerol 0.50 1.00 0.50 Glycerol3.00 7.50 7.50 2.50 Butylene glycol 10.00 Glycine soya 1.50 1.00 VitaminE acetate 0.50 0.20 0.25 0.75 1.00 α-Glycosylrutin 0.30 0.25 Butyloctylsalicylate 1.50 2,6-diethylhexyl naphthalate 3.50 Trisodium EDTA 0.300.10 0.20 Konkaben LMB ® 0.20 0.15 Methylparaben 0.50 0.15Phenoxyethanol 0.50 1.00 0.60 Ethanol 3.00 7.00 3.50 1.00 Insectrepellent 3535 7.50 Perfume 0.20 0.20 0.40 0.20 Dyes, water-soluble 0.02Water ad 100 ad 100 ad 100 ad 100 ad 100

7. Solids-stabilized emulsions 1 2 3 4 5 Mineral oil 16.00 16.00Octyldodecanol 9.00 9.00 5.00 Polyglyceryl-2 0.45 dipolyhydroxystearateCaprylic/capric triglyceride 9.00 9.00 6.00 C12–15-alkyl benzoates 5.008.00 Butylene glycol 8.00 dicaprylate/dicaprate Dicaprylyl ether 9.004.00 Dicaprylyl carbonate 9.00 Hydroxyoctacosanyl 2.00 2.00 2.00 2.001.50 hydroxystearate Disteardimonium hectorite 1.00 0.750 0.50 0.50 0.25Cera Microcristallina + Paraffinum 2.50 5.00 LiquidumHydroxypropylmethylcellulose 0.15 0.05 Dimethicone 4.50 UVASorb ® K2A2.00 5.00 3.00 1.50 1.00 Disodiumphenyldibenzimidazoletetrasulfonate3.00 1.00 2.00 Terephthalidenedicamphorsulfonic 2.00 0.50 acidPhenylbenzimidazolesulfonic acid 2.00 0.50 1.00 Uvinul ® A Plus 2.750.50 Ethylhexyl methoxycinnamate 6.00 3.0 Octocrylene 3.50 7.50Ethylhexyl salicylate 3.50 4.00 Diethylhexylbutamidotriazone 4.00 ParsolSLX ® 10.00 4.50 3.50 Benzophenone-3 2.50 0.50Methylenebis-benzotriazolyl 4.00 tetramethylbutylphenol Titanium dioxideEusolex ® T-2000 2.00 4.00 2.00 4.00 Titanium dioxide T 805 ® 3.00 Zincoxide NDM ® 6.00 Silica dimethyl silylate 1.00 Boron nitride 2.00 3.00Starch/sodium metaphosphate 0.5 polymer Tapioca starch 1.00 Sodiumchloride 1.00 1.00 1.00 1.00 Glycerol 5.0 10.0 6.00 10.0 IminosuccinateVP OC 370 ® 1.50 0.75 Trisodium EDTA 1.00 1.00 Methylparaben 0.21 0.20Propylparaben 0.07 Phenoxyethanol 0.50 0.40 0.40 0.50 Hexamidinediisethionate 0.08 Diazolidinylurea 0.28 0.28 Alcohol 5.00 2.50 Perfume0.45 0.20 0.45 Water ad 100 ad 100 ad 100 ad 100 ad 100

1. A light-protective cosmetic or dermatological preparation, comprising(a) at least one water-soluble UV filter substance and (b) at least onebenzoxazole derivative.
 2. The preparation as claimed in claim 1, asclaimed in claim 1,wherein the UV protection performance of thepreparation is higher than the predicted UV protection performance of(a) and (b).
 3. The preparation as claimed in claim 1, wherein the atleast one water-soluble filter substance includesphenylene-1,4-bis(2-benzimidazyl)-3,3′-5,5′-tetrasulfonic acidbis-sodium salt.
 4. The preparation as claimed in claim 1, wherein theat least one water-soluble filter substance includes at least onecompound selected from the group consisting of1,4-di(2-oxo-10-sulfo-3-bornylidenemethyl)benzene and its salts.
 5. Thepreparation as claimed in claim 1, wherein the preparation iswater-resistant.
 6. The preparation as claimed in claim 1, wherein theratio of the total concentration of the at least one water-soluble UVfilter substance to the total concentration of the at least onebenzoxazole derivative is from 5:1 to 1:5.
 7. The preparation as claimedin claim 1, further comprising at least one further UV filter substance.8. The preparation as claimed in claim 7, wherein the at least onefurther UV filter substance includes at least one UV filter substanceselected from the group consisting of triazines, benzotriazoles, organicpigments, and inorganic pigments.
 9. The preparation as claimed in claim7, wherein the at least one further UV filter substance includes atleast one UV filter substance selected from the group consisting of UVfilter substances that are liquid at room temperature.
 10. Thepreparation as claimed in claim 7, wherein the at least one further UVfilter substance includes at least one UV filter substance selected fromthe group consisting of dibenzoylmethane derivatives and2,4-bis{[4-(2-ethylhexyloxy)-2-hydroxy]phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine.11. The preparation as claimed in claim 10, wherein the at least one UVfilter substance includes 4-tert-butyl-4′-methoxydibenzoylmethane. 12.The preparation as claimed in claim 1, wherein the preparation isoil-free.
 13. The preparation as claimed in claim 1, further comprisingat least one flavone glycoside.
 14. The preparation as claimed in claim13, wherein the at least one flavone glycoside includes at least oneflavone glycoside selected from the group consisting of α-glycosylrutin,vitamin E, and vitamin E derivatives.
 15. The preparation as claimed inclaim 1, further comprising at least one self-tanning substance.
 16. Thepreparation as claimed in claim 15, wherein the at least oneself-tanning substance includes dihydroxyacetone.
 17. The preparation asclaimed in claim 1, further comprising at least one repellent.
 18. Thepreparation as claimed in claim 17, wherein the at least one repellentincludes ethyl 3-(N-n-butyl-N-acetylamino)propionate.
 19. Alight-protective cosmetic or dermatological preparation, comprising (a)at least one water-soluble UV filter substance and (b) at least onebenzoxazole derivative having the structural formula

wherein R¹, R², and R³, independently of one another, are selected fromthe group consisting of branched or unbranched, saturated or unsaturatedalkyl radicals having 1 to 10 carbon atoms.
 20. The preparation asclaimed in claim 19, wherein the at least one water soluble filtersubstance includes at least one filter substance selected from the groupconsisting of sulfonated water-soluble filter substances.
 21. Thepreparation as claimed in claim 20, wherein the at least one sulfonatedwater-soluble filter substance includesphenylene-1,4-bis(2-benzimidazyl)-3,3′-5,5′-tetrasulfonic acidbis-sodium salt.
 22. The preparation as claimed in claim 20, wherein theat least one sulfonated water-soluble filter substance includes at leastone compound selected from the group consisting of1,4-di(2-oxo-10-sulfo-3-bornylidenemethyl)benzene and its salts.
 23. Thepreparation as claimed in claim 19, wherein the at least one benzoxazolederivative includes2,4-bis[5-1(dimethylpropyl)benzoxazole-2-yl-(4-phenyl)imino]-6-(2-ethylhexyl)imino-1,3,5-triazine.24. The preparation as claimed in claim 19, wherein the preparation iswater-resistant.
 25. The preparation as claimed in claim 19, wherein theratio of the total concentration of the at least one water-soluble UVfilter substance (a) to the total concentration of the at least onebenzoxazole derivative (b) is from 5:1 to 1:5.
 26. The preparation asclaimed in claim 19, further comprising at least one UV filter substanceselected from the group consisting of dibenzoylmethane derivatives and2,4-bis{[4-(2-ethylhexyloxy)-2-hydroxy]phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine.27. The preparation as claimed in claim 19, further comprising4-tert-butyl-4′-methoxydibenzoylmethane.
 28. The preparation as claimedin claim 19, wherein the preparation is oil-free.
 29. The preparation asclaimed in claim 19, further comprising at least one UV filter substanceselected from the group consisting of UV filter substances that areliquid at room temperature.
 30. The preparation as claimed in claim 19,further comprising at least one self-tanning substance.
 31. Thepreparation as claimed in claim 30 wherein the at least one self-tanningsubstance includes dihydroxyacetone.
 32. The preparation as claimed inclaim 19, further comprising at least one repellent.
 33. The preparationas claimed in claim 32, wherein the at least one repellent includesethyl 3-(N-n-butyl-N-acetylamino)propionate.
 34. The preparation asclaimed in claim 19, further comprising at least one flavone glycoside.35. The preparation as claimed in claim 34, wherein the at least oneflavone glycoside includes at least one flavone glycoside selected fromthe group consisting of α glycosylrutin, vitamin E, and vitamin Ederivatives.
 36. A method of treating or preventing cosmetic ordermatological changes in the skin, comprising applying a cosmetic ordermatological preparation to the skin comprising (a) at least onewater-soluble UV filter substance and (b) at least one benzoxazolederivative.
 37. The method as claimed in claim 36, wherein the at leastone benzoxazole derivative has the structural formula

wherein R¹, R², and R³, independently of one another, are selected fromthe group consisting of branched or unbranched, saturated or unsaturatedalkyl radicals having 1 to 10 carbon atoms.
 38. The method as claimed inclaim 37, wherein the at least one benzoxazole derivative includes2,4-bis[5-1(dimethylpropyl)benzoxazole-2-yl-(4-phenyl)imino]-6-(2-ethylhexyl)imino-1,3,5-triazine.39. The method as claimed in claim 36, wherein the at least onewater-soluble filter substance includes at least one UV filter substanceselected from the group consisting of sulfonated water-soluble filtersubstances.
 40. The method as claimed in claim 39, wherein the at leastone water-soluble filter substance includesphenylene-1,4-bis(2-benzimidazyl)-3,3′-5,5′-tetrasulfonic acidbis-sodium salt.
 41. The method as claimed in claim 39, wherein the atleast one water-soluble filter substance includes at least one compoundselected from the group consisting of1,4-di(2-oxo-10-sulfo-3-bornylidenemethyl)benzene and its salts.
 42. Amethod of tanning or accelerating tanning of the skin, comprisingapplying a cosmetic or dermatological preparation to the skin comprising(a) at least one water-soluble UV filter substance and (b) at least onebenzoxazole derivative.
 43. The method as claimed in claim 42, whereinthe at least one benzoxazole derivative has the structural formula

wherein R¹, R², and R³, independently of one another, are selected fromthe group consisting of branched or unbranched, saturated or unsaturatedalkyl radicals having 1 to 10 carbon atoms.
 44. The method as claimed inclaim 43, wherein the at least one benzoxazole derivative includes2,4-bis[5-1(dimethylpropyl)benzoxazole-2-yl-(4-phenyl)imino]-6-(2-ethylhexyl)imino-1,3,5-triazine.45. The method as claimed in claim 42, wherein the at least onewater-soluble filter substance includes at least one filter substanceselected from the group consisting of sulfonated water-soluble filtersubstances.
 46. The method as claimed in claim 45, wherein the at leastone water-soluble filter substance includesphenylene-1,4-bis(2-benzimidazyl)-3,3′-5,5′-tetrasulfonic acidbis-sodium salt.
 47. The method as claimed in claim 45, wherein the atleast one water-soluble filter substance includes at least one compoundselected from the group consisting of1,4-di(2-oxo-10-sulfo-3-bornylidenemethyl)benzene and its salts.
 48. Themethod as claimed in claim 42, further comprising at least oneself-tanning substance.
 49. The method as claimed in claim 48, whereinthe at least one self-tanning substance includes dihydroxyacetone.
 50. Amethod of protecting the skin against light-induced aging, comprisingapplying a cosmetic or dermatological preparation to the skin comprising(a) at least one water-soluble UV filter substance and (b) at least onebenzoxazole derivative.
 51. The method as claimed in claim 50, whereinthe at least one benzoxazole derivative has the structural formula

wherein R¹, R², and R³, independently of one another, are selected fromthe group consisting of branched or unbranched, saturated or unsaturatedalkyl radicals having 1 to 10 carbon atoms.
 52. The method as claimed inclaim 51, wherein the at least one benzoxazole derivative includes2,4-bis[5-1(dimethylpropyl)benzoxazole-2-yl-(4-phenyl)imino]-6-(2-ethylhexyl)imino-1,3,5-triazine.53. The method as claimed in claim 50, wherein the at least onewater-soluble filter substance includes at least one filter substanceselected from the group consisting of sulfonated water-soluble filtersubstances.
 54. The method as claimed in claim 53, wherein the at leastone water-soluble filter substance includesphenylene-1,4-bis(2-benzimidazyl)-3,3′-5,5′-tetrasulfonic acidbis-sodium salt.
 55. The method as claimed in claim 53, wherein the atleast one water-soluble filter substance includes at least one compoundselected from the group consisting of1,4-di(2-oxo-10-sulfo-3-bornylidenemethyl)benzene and its salts.
 56. Themethod as claimed in claim 50, wherein the preparation further comprisesat least one UV filter substance selected from the group consisting ofUV filter substances that are liquid at room temperature.
 57. The methodas claimed in claim 50, wherein the preparation further comprises atleast one UV filter substance selected from the group consisting ofdibenzoylmethane derivatives and2,4-bis{[4-(2-ethylhexyloxy)-2-hydroxy]phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine.58. The method as claimed in claim 57, wherein the dibenzoylmethanederivative is 4-tert-butyl-4′-methoxydibenzoylmethane.
 59. The method asclaimed in claim 50, wherein the preparation further comprises at leastone flavone glycoside.
 60. The method as claimed in claim 59, whereinthe at least one flavone glycoside includes at least one flavoneglycoside selected from the group consisting of α glycosylrutin, vitaminE, and vitamin E derivatives.
 61. A cosmetic or dermatological wipecomprising a water-insoluble substrate impregnated with a preparationcomprising (a) at least one water-soluble UV filter substance and (b) atleast one benzoxazole derivative.
 62. The wipe as claimed in claim 61,wherein the at least one benzoxazole derivative has the structuralformula

wherein R¹, R², and R³, independently of one another, are selected fromthe group consisting of branched or unbranched, saturated or unsaturatedalkyl radicals having 1 to 10 carbon atoms.
 63. The wipe as claimed inclaim 62, wherein the at least one benzoxazole derivative includes2,4-bis[5-1(dimethylpropyl)benzoxazole-2-yl-(4-phenyl)imino]-6-(2-ethylhexyl)imino-1,3,5-triazine.64. The wipe as claimed in claim 61, wherein the at least onewater-soluble filter substance includes at least one filter substanceselected from the group consisting of sulfonated water-soluble filtersubstances.
 65. The wipe as claimed in claim 64, wherein the at leastone water-soluble filter substance includesphenylene-1,4-bis(2-benzimidazyl)-3,3′-5,5′-tetrasulfonic acidbis-sodium salt.
 66. The wipe as claimed in claim 64, wherein the atleast one water-soluble filter substance includes at least one compoundselected from the group consisting of1,4-di(2-oxo-10-sulfo-3-bornylidenemethyl)benzene and its salts.